Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
  • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
  • C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids

Definitions

• the invention relates to polyester polyols of a defined type, to their manufacture by esterification or transesterifcation of polyether polyols also of a defined type, with certain polybasic acid species and their conversion to polyurethanes by reaction with polyisocyanates.
• R 2 is --H, --CH 2 OH, or --CH 2 C(CH 2 OH) 3
• a polyhydric alcohol is present, other than one of the type defined above, it is preferably incorporated into the composition such that after alkoxylation the alkoxylated derivative forms at least 5% by weight of the polyether polyol composition and the polyhydric alcohol has the general formula (II) or is a mixture of compounds of that formula.
• R 3 and R 4 which may be the same or different, are selected from --H, --CH 2 OH and --CH 2 OCH 3 provided that only one of R 3 or R 4 may be --CH 2 OCH 3
• R 5 is --OH, --OCH 2 OH or --OCH 2 C(CH 2 OH) 3 .
• a preferred polyether polyol comprises 10 to 95% of oxyalkylated polyhydric alcohols according to formula I and 5 to 50% of oxyalkylated polyhydric alcohols according to formula (II).
• the alkoxylation agent could be propylene oxide, ethylene oxide or butylene oxide or mixtures thereof.
• polyester derivatives of the above polyols provide new polyols of improved processability suitable for the manufacture of rigid polyurethane foams of fine cell-structure.
• polyols are manufactured from two readily available starting components.
• the latter are indeed waste byproducts from the manufacture of pentaerythritol on one side and adipic acid or terephthalic acid or derivatives thereof on the other side.
• the polybasic acid species used in the preparation of the polyester polyols of the invention include:
• aromatic dibasic acids of the general formula ##STR3## wherein R is H, methyl or ethyl and carboxyl groups are in the ortho, meta or para positions relative to each other or mixtures thereof, preferably dimethyl terephthalate or distillation residues therefrom, residues from polyethylene terephthalate (PET) manufacture or product from the recycle of PET waste,
• PET polyethylene terephthalate
• Tetrabutyl-o-titanate was used for this invention and is a known catalyst for esterification/transesterification reactions; other catalysts could include stannous octoate or p-toluene sulphonic acid.
• polyester polyol of the present invention with an average hydroxyl value in the range 250 to 400 mg KOH/g and with a weight average functionality in the range 2.3 to 5, may be used in admixture with known polyether polyols, polyester polyols or polyesteramide polyols.
• the present invention includes also the manufacture of polyurethane products, for example polyurethane foams, in known manner, from the polyester polyols described above, and also includes polyurethane products so prepared.
• Polyurethane products are made by reacting a di- or polyisocyanate with the described polyester polyol.
• the nature of the polyurethane product, for example the polyurethane foam may be varied depending on a variety of factors such as the functionality of the reactants and the presence of active ingredients.
• the organic di- or polyisocyanates may be any of the isocyanates known to be useful for the formation of polyurethane products such as polyurethane foams.
• aromatic di- or polyisocyanates for example tolylene diisocyanate and especially diphenylmethane diisocyanate (MDI) which are commercialy available in a variety of forms.
• MDI diphenylmethane diisocyanate
• Suitable diphenylmethane di-isocyanates include
• polymers and oligomers obtained by reacting diphenylmethane diisocyanates or polymeric MDI with a monomeric glycol or polyhydric alcohol (or mixtures thereof) or with a hydroxyl-ended polyester or polyether and known as ⁇ MDI prepolymers ⁇ ;
• the preparation of the foamed polyurethane materials may be carried out by the general methods fully described elsewhere.
• the foam forming components may be mixed continuously or discontinuously in the presence of the gas generating agent to give a foam.
• the foam forming gas may be generated by a variety of methods.
• the gas may be carbon dioxide generated by the reaction of a proportion of the organic isocyanate with water incorporated in the reaction mixture.
• Gas may also be generated by incorporating in the reaction mixture an inert liquid of low boiling point which vaporises during the exothermic polyurethane foaming reaction.
• inert liquid of low boiling point which vaporises during the exothermic polyurethane foaming reaction.
• Mixtures of water with inert low boiling point liquids may be used if desired.
• examples of such liquids are halogenated hydrocarbons such as methylene chloride, halomethanes and haloethanes. Mixtures of these low boiling point liquids one with another and/or with other substituted or unsubstituted hydrocarbons may also be used.
• Such liquids are usually employed in amounts of from 5% to 50% by weight of the polyester polyol.
• Water is usually employed in amounts of from 1% to 10% by weight of the polyester when used as a gas generating agent.
• Catalysts for the polyurethane forming reaction may also be included, especially tertiary-amines, basic compounds and metal compounds.
• Foam stabilisers such as siloxane alkoxy-ether copolymers may be present, together with additives such as pigments, flame retardants, fillers, chain extenders, crosslinking agents, plasticisers and anti-oxidants, each being used alone or in combination with the other additives.
• polyester polyols prepared according to the present invention are given below but could also include use of adipic acid, dimethyl terephthalate and the starting polyether polyols could also be prepared solely using ethylene oxide or mixture of ethylene-oxide/propylene oxide both by sequential or concurrent addition.
• a nitrogen sparge was established through the reactor contents at a rate of 62 l/h with agitation.
• the reactor was fitted with a reflux/fractionation column packed with 5 mm ceramic Raschig rings. Vapour from the top of the column passed through an air/water condenser system to a suitable calibrated receiver.
• the reactor contents were heated to 200-210 deg C. at which temperature, methanol commenced distilling from the column top. 650 parts total distillate were recovered over 6 h during which time the reactor contents had reached 230 deg C.; the column head temperature remained constant at 60-65 deg C.
• the prepared polyester polyols from Examples 1 to 2 above were co-blended with (a) their based polyether polyols (A and B) respectively or (b) polyether polyol (E), a high functional sucrose amine product of hydroxyl value 575 mg KOH/g or (c) a combination of (a) or (b) as detailed in the Table.
• the average hydroxyl value of the polyol blend is mentioned.
• polyurethane rigid foams made from the polyester polyol blends and their parent polyether polyol or sucrose-amine polyether or mixtures thereof, are also described in Examples 3 to 7 in the Table.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Polyesters Or Polycarbonates (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Publications (1)

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Cited By (8)

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Citations (7)

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• 1985
  • 1985-02-18 GB GB858504096A patent/GB8504096D0/en active Pending
• 1986
  • 1986-01-15 AT AT86300244T patent/ATE47411T1/de not_active IP Right Cessation
  • 1986-01-15 DE DE8686300244T patent/DE3666445D1/de not_active Expired
  • 1986-01-15 EP EP86300244A patent/EP0192325B1/en not_active Expired
  • 1986-01-22 ZA ZA86488A patent/ZA86488B/xx unknown
  • 1986-01-24 US US06/822,132 patent/US4758606A/en not_active Expired - Fee Related
  • 1986-01-24 AU AU52718/86A patent/AU578513B2/en not_active Ceased
  • 1986-01-30 CA CA000500785A patent/CA1263494A/en not_active Expired
  • 1986-02-13 DK DK070186A patent/DK70186A/da not_active Application Discontinuation
  • 1986-02-18 JP JP61033681A patent/JPS61192726A/ja active Pending

Patent Citations (7)

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